Computational and Theoretical Chemistry最新文献

{"title":"Insights on formation of oxide layers, corrosion, and hydrogen embrittlement on the Ti2AlNb (1 1 0) surface: Density functional theory study","authors":"D.M. Tshwane ,&nbsp;P.M. Maleka ,&nbsp;R.S. Dima ,&nbsp;L. Mogakane ,&nbsp;T. Ngcobo ,&nbsp;R.R. Maphanga","doi":"10.1016/j.comptc.2024.115002","DOIUrl":"10.1016/j.comptc.2024.115002","url":null,"abstract":"<div><div>Ti₂AlNb alloys offer good mechanical qualities and promise for use in various applications, such as aero-engines and other industries. However, corrosion and hydrogen embrittlement remain important concerns and limitations for their use. In this work, first-principle density functional theory is used to investigate the adsorption of hydrogen, fluorine and oxygen on the surface of Ti₂AlNb (1<!--> <!-->1<!--> <!-->0). The effects of the considered adsorbates on the surface were compared by analysing the adsorption energy, charge density differences, density of states, and work function. The current findings revealed that the adsorption behaviour of all the adsorbates is exothermic and spontaneous due to the negative adsorption energy. More importantly, the effect of Van der Waals forces and dispersion correction was considered, it was found that for all adsorbates the dispersion correction approach exhibited the most stable adsorption energies (<span><math><mrow><msubsup><mi>E</mi><mrow><mi>ads</mi></mrow><mrow><mi>DFT</mi><mo>-</mo><mi>D</mi></mrow></msubsup></mrow></math></span>) than the standard density functional theory (<span><math><mrow><msubsup><mi>E</mi><mrow><mi>ads</mi></mrow><mrow><mi>DFT</mi></mrow></msubsup></mrow></math></span>). Thus, the standard DFT underestimates the adsorption energy. Furthermore, it was shown that the adsorption energy strength is dependent on the surface adsorption site, with the Ti-Nb and Al-Nb bridge sites being the most preferred sites for hydrogen, fluorine and oxygen adsorption. Subsequently, it was discovered that oxygen adsorption on the surface of Ti₂AlNb (1<!--> <!-->1<!--> <!-->0) was more thermodynamically stable than hydrogen and fluorine. This suggests that the Ti₂AlNb surface will likely suffer from oxidation rather than corrosion and hydrogen embrittlement. In addition, surface atoms showed electron-charge depletion, while adsorbates showed charge accumulation. The adsorption caused charge density redistribution and altered the surface work function.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115002"},"PeriodicalIF":3.0,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142746123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Geometrical features, stability and hydrogen positions in (Al2Cu)n clusters","authors":"Xi Wang ,&nbsp;Yule Yan ,&nbsp;Qiman Liu","doi":"10.1016/j.comptc.2024.114999","DOIUrl":"10.1016/j.comptc.2024.114999","url":null,"abstract":"<div><div>The phase equilibria of the Al-Cu alloys have been well-established, with the Al₂Cu being a crucial component of the phase diagram. Constructing an atomic model with a 2:1 stoichiometric ratio of Al and Cu holds significance for further investigating the local structures of the alloy phases. Here, we employ the GA-DFT method to explore the structural potential energy surfaces of (Al₂Cu)_n clusters (n = 1–6). The results reveal that the (Al₂Cu)_n evolve from hollow cages to more densely packed configurations, with Al atoms relatively more concentrated and Cu atoms becoming more dispersed throughout the structures. The <em>E</em>_b and Δ₂<em>E</em> analyses show that the (Al₂Cu)₃ has a higher stability than that of its neighbors, and the AIMD simulations demonstrate that it can maintain the structural integrity at 700 K. The molecular orbitals reveal that 21 valence electrons of the (Al₂Cu)₃ fill superatomic orbits resulting in an electronic configuration of 1S²1P⁶1D¹⁰2S²1F¹, which is also confirmed by the density of states. The good stability of the (Al₂Cu)₃ allows the bonding of the H atom to it without causing significant deformation changes in the parent geometry, in which the H tends to preferentially locate at Al sites. The deformation of structures is particularly obvious when H is close to Cu atom.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114999"},"PeriodicalIF":3.0,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142745387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"N-Boron-pyrrole: A negative charge stabilizing group","authors":"Younes Valadbeigi","doi":"10.1016/j.comptc.2024.115000","DOIUrl":"10.1016/j.comptc.2024.115000","url":null,"abstract":"<div><div>We show that the N-boron-pyrrole (B-pyrrole) group stabilizes the negatively charged compounds, despite not being an electron withdrawing group (EWG). Density functional theory (DFT) calculations revealed that this distinctive property of the B-pyrrole group arises from enhanced π-electron delocalization within the pyrrole ring. The effect of B-pyrrole group on the Brønsted and Lewis acidity of various compound classes was examined and compared with common EWGs including F, Cl, Br, CN, NO₂. Substitution of pyrrole into the boracyclohexadiene derivatives enhances their acidity by about 1–6 kcal mol⁻¹ while the acidity enhancement due to pyrrole substitution into boric acid was about 17 kcal mol⁻¹. Interestingly, B(Pyrrole)₃ exhibited a fluoride affinity comparable to BF₃ (∼78 kcal mol⁻¹) and approximately 15 kcal mol⁻¹ higher than that of BH₃.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 115000"},"PeriodicalIF":3.0,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142745384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A quantum investigation of kinetic isotope effects in the Ne + HD+(v=0) → NeH+/NeD+ + D/H reaction","authors":"Hui Wu ,&nbsp;Xiaohu He ,&nbsp;Zhixin Duan","doi":"10.1016/j.comptc.2024.114994","DOIUrl":"10.1016/j.comptc.2024.114994","url":null,"abstract":"<div><div>The exact quantum scattering calculations for the Ne + HD<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span>(<em>v</em> = 0, <em>j</em> = 0) reaction on its electronic ground state have been performed using the time-dependent wave packet method at the state-to-state level. The reaction mechanisms and intramolecular isotope effects have been investigated and analyzed in terms of integral reaction cross section, product internal state distributions and differential cross sections in the 0.4–1.2 eV collision energy interval. Results from the present calculations show that the products NeH<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span> and NeD<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span> are associated to different values of the total angular momentum, <em>J</em>. Competing reaction mechanisms that correlate with low and high <em>J</em> values show different preferences for products.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114994"},"PeriodicalIF":3.0,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular adsorption of chloromethane and vinyl chloride on square lattice net phosphorene – A first-principles study","authors":"V. Nagarajan,&nbsp;R. Bhuvaneswari,&nbsp;R. Chandiramouli","doi":"10.1016/j.comptc.2024.114996","DOIUrl":"10.1016/j.comptc.2024.114996","url":null,"abstract":"<div><div>The advancement of two-dimensional (2D) materials after the discovery of graphene leads to the path of various 2D materials. One such 2D material is square lattice (sql) net phosphorene. Initially, the structural and dynamic stability of sql phosphorene is confirmed with regard to the formation energy and phonon-band-spectrum. The electronic properties of sql phosphorene are explored using band structure and projected density of states spectrum. Besides, the calculated band gap value of sql phosphorene is 3.174 eV which shows the semiconducting nature of the material. Owing to the structural firmness and semiconducting nature of sql phosphorene material, it is used as a sensing element for chloromethane and vinyl chloride molecules. Evidently, the adsorption of chloromethane and vinyl chloride on sql phosphorene leads to modulating the energy band gap, electron difference density, and charge transfer, which infers changes in the electronic properties of sql phosphorene. The adsorption energy range is recorded to be −0.152 eV to −0.608 eV which confirms that the chloromethane and vinyl chloride are physisorbed on sql phosphorene. The findings ensure that sql phosphorene is a proper sensing element for the detection of chloromethane and vinyl chloride molecules.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 114996"},"PeriodicalIF":3.0,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142746124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular dynamics insight of interaction between Artemisinin and its derivatives and the cancer cell membrane","authors":"Samaneh Boroomand ,&nbsp;Delara Mohammad-Aghaie ,&nbsp;Fatemeh Mohammadpour","doi":"10.1016/j.comptc.2024.114997","DOIUrl":"10.1016/j.comptc.2024.114997","url":null,"abstract":"<div><div>In the present study, a molecular dynamics simulation approach has been utilized to investigate the effectiveness of four molecules, including Artemisinin, a natural product, and its derivatives Dihydroartemisinin, Artesunate, and Artemisone, on a membrane of a cancerous cell. Performed simulations predicted that Dihydroartemisinin and Artemisone form stronger hydrogen bonds with the cancer membrane, exhibit higher mobility, and have a longer lifetime at the water-membrane interface. Artemisone molecules could penetrate the hydrophobic part of the lipid’s tail, leading to higher fluidity of the cancer membrane. These two compounds exerted the greatest effect on the properties and characteristics of the membrane model while showing stronger anti-cancer effects than the other two compounds. The simulation outcomes and predictions were found to agree with the results of experimental studies. It is noticeable that Dihydroartemisinin and Artemisone enter the cancer cell membrane from their functional group side, while Artemisinin and Artesunate enter from their peroxide ring side.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114997"},"PeriodicalIF":3.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142745385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational investigation of magnetic field effect on thermal function of diatomic molecules with anharmonic oscillator potential","authors":"Ahmad Ghanbari","doi":"10.1016/j.comptc.2024.114991","DOIUrl":"10.1016/j.comptc.2024.114991","url":null,"abstract":"<div><div>In the present study, I have investigated the magnetic field contributions on thermal properties of diatomic molecules such as H₂, HCl and CO with isotropic oscillator plus inverse quadratic potential. To this end, I have solved the Schrödinger equation with the potential model in the presence of magnetic fields and have obtained bound states of the system via the Laplace transform approach. Applying the determined energy eigenvalues, I have computed the partition function and thermal function such as specific heat in constant pressure, Gibbs free energy and enthalpy in the presence of external magnetic field using Poisson summation formula. I have compared our results with experimental data and there is a good agreement between them. I have computed the average absolute deviations of specific heat in constant pressure, Gibbs free energy and enthalpy for diatomic molecules in the presence and absence of magnetic fields. All calculated average deviations are under 3 % that show our accuracy of computations. My results show that external magnetic fields have a significant influence on thermodynamic properties of diatomic molecules.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114991"},"PeriodicalIF":3.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142698694","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dopamine interaction with DNA/RNA aptamers: Molecular dynamics simulation","authors":"Majid Sharifian,&nbsp;Tahereh Heidari,&nbsp;Mohammad Razmkhah,&nbsp;Fatemeh Moosavi","doi":"10.1016/j.comptc.2024.114990","DOIUrl":"10.1016/j.comptc.2024.114990","url":null,"abstract":"<div><div>One method for detecting dopamine involves the use of RNA and DNA aptamers. Aptamers are single-stranded sequences of DNA or RNA that bind with high affinity to specific target molecules. Various aptamers have been developed to measure dopamine, making it crucial to identify which one exhibits the strongest interaction with it. This study, for the first time, examines the interaction between dopamine and aptamers using molecular dynamics simulations. The findings reveal that all three aptamers can interact with and detect dopamine. By calculating the binding Gibbs energy (ΔG_bind) between the aptamers and dopamine, it was determined that the DNA aptamer with 44 nucleotide residues is the most selective for dopamine. Additional analyses of the root-mean-square deviation (RMSD), root-mean-square fluctuation (RMSF), radial distribution function (RDF), and radius of gyration (R_g) which assess structural stability and fluctuations further support that this aptamer has the most effective interaction with dopamine.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114990"},"PeriodicalIF":3.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT insights into multifaceted properties of GaCaX3 (X = Cl, Br, I) inorganic cubic halide perovskites for advanced optoelectronic applications","authors":"Muhammad Riaz ,&nbsp;Syed Mansoor Ali ,&nbsp;N. Bano ,&nbsp;Syed Danish Ali ,&nbsp;Muhammad Asif Shakoori","doi":"10.1016/j.comptc.2024.114993","DOIUrl":"10.1016/j.comptc.2024.114993","url":null,"abstract":"<div><div>Halide perovskites, known for their outstanding properties and flexible chemistry, gained considerable attention in diverse fields. This study explores the structural, optoelectronic, thermodynamic, and mechanical characteristics of the inorganic cubic halide perovskites, GaCaX₃ (X = Cl, Br and I) using DFT within the CASTEP framework. Electronic analysis determined band gaps of GaCaCl₃ (4.67 eV), GaCaBr₃ (3.89 eV), and GaCaI₃ (2.97 eV) respectively. Bond population analysis indicated that GaCaI₃ provides accurate electronic bond description with minimal charge loss (0.15 %). Optically, GaCaI₃ shows significant absorption, while GaCaCl₃ indicate strong plasmonic behavior, high refractive index and reflectivity. Mechanical stability confirmed through Born-stability condition through elastic constants (C₁₁, C₁₂, and C₄₄). Poisson’s ratio (n), Pugh’s ratio (B/G), and anisotropic factor further emphasize the ductility and anisotropic behavior for all materials. Also, bulk modulus (B), shear modulus (G), and Young’s modulus (E), follow the as GaCaCl₃ &gt; GaCaBr₃ &gt; GaCaI_3, respectively. From thermodynamic characteristics, GaCaCl₃ exhibits the maximum enthalpy, free energy, entropy, heat capacity, and Debye temperature indicating superior thermal stability. Confidently, these outstanding properties of GaCaX₃ (X = Cl, Br and I) halide perovskites hold significant potential for advanced optoelectronic devices.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114993"},"PeriodicalIF":3.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142698692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigating optical, electronic, and thermoelectric properties of X2ScIO6 (X = K, Rb, and Cs) double perovskite semiconductors for green energy applications","authors":"Saleh Hayat ,&nbsp;Mansoor Ahmad Khan ,&nbsp;Malak Azmat Ali ,&nbsp;Afzal Khan ,&nbsp;Razan A. Alshgari ,&nbsp;Saikh Mohammad ,&nbsp;Samah Al-Qaisi","doi":"10.1016/j.comptc.2024.114992","DOIUrl":"10.1016/j.comptc.2024.114992","url":null,"abstract":"<div><div>We present our findings on the structural, optical, electronic, and thermoelectric characteristics of X₂ScIO₆ (X = K, Rb, and Cs) double perovskites using density functional theory (DFT) and post-DFT calculations. The calculated tolerance factor values exhibit the structural stability of these double perovskites, whereas negative values of the formation energy and Gibbs free energy verify their thermodynamic stability. Energy band structure calculations reveal the<!--> <!-->semiconducting nature of these perovskites with band gaps of 1.37, 1.03, and 0.55 eV for K₂ScIO₆, Rb₂ScIO_6, and Cs₂ScIO₆ respectively. These double perovskites could achieve higher optical absorption in the ultraviolet region beyond 5 eV. The Seebeck coefficient’s positive value indicates these compounds’ p-type nature. Their figure of merit values are greater than the other conventional double perovskites and therefore could be efficiently utilized in thermoelectric applications at elevated temperatures.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114992"},"PeriodicalIF":3.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}